Composition and method for treating substrates to reduce electrostatic charge and resultant article

ABSTRACT

Antistatic agents and their use in processing textiles or formed plastic substrates. The antistatic agent comprises a compound having a fluorocarbon moiety and an ethoxylated quaternary ammonium moiety. The antistatic composition increases the electrolytic conductivity of treated textile or plastic materials, thereby increasing the rate of electrostatic charge dissipation thereof. The antistatic agents remain effective after exposure of the treated substrate to an aqueous environment.

This application is a division of application Ser. No. 08/154,665, filedNov. 18, 1993, now U.S. Pat. No. 5,478,486.

FIELD OF THE INVENTION

The present invention relates to antistatic agents and their use intextile and plastics processing.

BACKGROUND OF THE INVENTION

Electrostatic charge is the result of electrification of an object suchthat the charge is confined to the object. Friction between two surfacesin close contact typically gives rise to electrostatic charge or staticelectricity.

Textiles and plastics generally have low conductivity and dissipatecharge at a relatively low rate. While it has been proposed to attenuateelectrostatic charge build-up on textile and plastic materials byreducing its rate of generation, friction is inherent in many plasticsand textile processing operations, particularly the latter, and cannotbe substantially reduced. Consequently, increasing the rate ofelectrostatic charge dissipation of a textile or plastic material byincreasing its electrolytic conductivity through the application ofinternal or external antistatic agents is commonly used as a means ofcontrolling electrostatic build-up in such materials.

External or surface antistatic agents are directly applied as a coatingto the surface layer of a textile or formed plastic substrate, typicallydissolved or suspended in a suitable vehicle, such as water or anothersolvent. Internal antistatic agents are commonly used in formed plasticsubstrates and are physically mixed or blended with the resin mass priorto the forming operation, e.g., spinning, drawing, molding or the like,so as to be uniformly distributed throughout the body of the finishedproduct, including the surface layer. Internal antistatic agentsgenerally provide a longer lasting electrostatic charge dissipativeeffect.

Various chemicals have been proposed for use as antistatic agents,including, by way of example, long-chain amines, amides and quaternaryammonium salts; esters of fatty acids and their derivatives; sulfonicacids and alkyl aryl sulfonates; polyoxyethylene derivatives;polyglycols and their derivatives; polyhydric alcohols and theirderivatives; and phosphoric acid derivatives.

Treatment of polyester and nylon fabrics with antistatic agents has beenshown to reduce soiling. Static-prone plastic articles, such aspackaging materials, that are treated with antistatic agents resistaccumulation of dust and thus are more attractive for packaging ofconsumer products. Moreover, static charged plastic packaging and otherplastic products have the potential to cause damage to semiconductorchips and constitute a possible explosion hazard in areas whereflammable gases are used.

Ideally, surface antistatic agents used in textile and plasticsprocessing are stable and not transient. That is to say, an amount ofantistatic agent sufficient to provide effective electrostatic chargedissipation is retained on the surface of the coated substrate, whethertextile or plastic, until processing is complete. Such processing ofteninvolves exposure of the treated textile or plastic to an aqueousenvironment, which tends to reduce the amount of antistatic agentpresent on the treated surface, thus diminishing its static dissipativeeffect. The use of stable antistatic agents offers the advantage ofobviating repeated application of the antistatic agent to thestatic-prone substrate during processing.

Antistatic agents are also used for enhancing the receptivity of plasticsurfaces to electrostatically applied coatings, e.g., in automobileproduction. See, for example, U.S. Pat. No. 5,219,493. In thisapplication also, it is desirable that the antistatic agent resistsremoval when exposed to an aqueous rinse or wash liquid.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide an antistatic agentcapable of effectively dissipating electrostatic charge from astatic-prone object treated therewith.

It is a further object of this invention to provide an antistatic agentfor internal or external application to textile and plastic substrates.

It is another object of this invention to provide an antistatic agentproviding a relatively long lasting electrostatic charge dissipativeeffect to substrates treated therewith, even after exposure of thetreated substrate to an aqueous environment, such as aqueous rinse orwash liquid.

It has surprisingly been found that the above objects are achievable bymeans of the antistatic agent of the present invention which comprises,or preferably consists essentially of a compound of the formulaQ--L--(R--X)_(d), wherein Q represents a normal or branched, saturatedor unsaturated perfluoroaliphatic radical, L represents an ester or anether linkage, R represents an alkylene-oxyalkylene or analkylene-poly(oxyalkylene) group, and X represents at least onequaternary ammonium group of the formula ##STR1## and, optionally, atertiary amine group of the formula ##STR2## wherein R₁ and R₄independently represent --(C₂ H₄ O)_(f) --Z, Z being H, Q or ##STR3## fbeing an integer from 1 to 50, R₂ represents a C₁ -C₄ alkyl group, R₃and R₅ independently represent a normal or branched, saturated orunsaturated C₆ -C₂₂ aliphatic group, A represents an organic orinorganic anion and d is 1 or 2.

The reaction mixture that results from preparation of the aforesaidcompound is applicable, as is, for antistatic treatment of varioussubstrates. The working composition thus contains unreacted startingmaterials if present in stoichiometric excess, and may contain some orall of the medium in which the reaction is conducted. Of course, one ormore additional components, such as solvents, may be included in thecomposition, e.g., to assist in solubilizing the compound, or in dryingof the composition on the treated substrate. It is an advantage of thecomposition of the invention that isolation and recovery of theantistatically active agent from the reaction mixture is obviated.

The present invention also provides a method for dissipatingelectrostatic charge on a static-prone substrate by incorporating intothe substrate, either internally or externally, the antistatic agent ofthe invention in an amount effective to impart to the substrate asurface resistance value in the range of from about 10⁶ to about 10¹²ohms, a 90% electrostatic charge decay time of 10 seconds or less, orboth.

Also in accordance with the present invention, there are providedarticles of manufacture including textile, thermoplastic and thermosetsubstrates which are treated with the composition of the invention andeffectively dissipate static electricity.

The composition and method of the invention are also useful forimparting a desired level of surface conductivity to formed plasticarticles, such as automobile bumper parts, for electrostatically appliedcoating materials, resulting in good adhesion of the coating material tothe treated article.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, "antistatic agent" refers to a substance, or mixture ofsubstances, added to a material, either internally or externally, tomake the material static dissipative. The term "static-prone" refers tosubstrates that are susceptible to development of electrostatic charge,due to the way in which they are processed, or otherwise.

The antistatic composition of the invention is the product of a chemicalreaction between a compound comprising a fluorocarbon radical and apolyalkoxylated quaternary ammonium compound and, optionally, apolyalkoxylated tertiary amine.

The reaction product preferably comprises an ester formed by thereaction of at least one normal or branched, saturated or unsaturatedperfluoroaliphatic carboxylic acid and a hydroxyl-substituted,ethoxylated quaternary ammonium compound. Alternatively, however, theester may be the product of the reaction of a fluoroalcohol with anethoxylated quaternary ammonium compound having one or more terminalcarboxyl groups. Ether compounds of the type mentioned above may beprepared by fluorinated "capping" of hydroxyl-terminated,polyethoxylated quaternary ammonium compounds with tetrafluoroethyleneoxide or heptafluoropropylene oxide, according to procedures known inthe art.

The fluorocarbon-containing compound is preferably of the formula (C_(q)F_(2q+1))--COOH, wherein q represents an integer from 1 to 17.Representative examples of such acids include perfluoro-acetic,propionic, butyric, pentanoic, hexanoic, heptanoic, octanoic, nonanoicand decanoic acids. The perfluorocarboxylic acids may contain mixturesof various chain lengths, depending upon their method of manufacture,and the use of such mixtures is within the scope of this invention.

Suitable hydroxyl-substituted, polyethoxylated quaternary ammoniumcompounds for use in forming the antistatic composition of the inventioninclude those of the formula ##STR4## wherein g and k are each integersfrom 1 to 50, preferably 2-16, which may be the same or different, j isan integer from 1 to 4, preferably 1 or 2, R₆ represents a normal orbranched, saturated or unsaturated C₆ -C₂₂ aliphatic group, preferablyC₆ -C₁₈, and A is an organic or inorganic anion, preferably halide,sulfate, lower alkyl sulfate or the like. The term "aliphatic" as usedherein refers not only to groups that are exclusively hydrocarbons,i.e., paraffins, olefins and acetylenes, but also to derivatives thereofincluding one or more ether linkage.

Preferred hydroxyl-substituted polyethoxylated quaternary ammoniumcompounds for use in forming the antistatic composition of the inventioninclude those of the formula ##STR5## wherein s and w may be the same ordifferent and are each integers from 2-16; t is 1 or 2; R₈ represents anormal or branched, saturated or unsaturated C₆ -C₁₈ aliphatic group;and A represents an anion selected from the group consisting ofchloride, sulfate and lower alkyl sulfate.

Examples of the preferred quaternary ammonium compounds are ethylbis(polyethoxyethanol) tallow ammonium salt, methyl bis(polyethoxyethanol) coco ammonium salt and polyethoxy coco ether aminediethylsulfate ammonium salt.

Most preferred are ethyl bis(polyethoxyethanol) tallow ethyl sulfateammonium salt, available from Witco Corporation, under the trademarkVariquat® 66 and methyl bis(polyethoxy ethanol) coco ethoxylatedchloride ammonium salt, available from Witco Corporation under theproduct designation Variquat® K-1215.

Ethoxylated tertiary fatty amines of the formula ##STR6## wherein m andn are each integers from 1 to 50, preferably 2-16, which may be the sameor different, R₇ represents a normal or branched, saturated orunsaturated, C₆ -C₂₂ aliphatic group, preferably C₆ -C₁₈, may optionallybe included as reactants forming the antistatic composition of theinvention, in combination with quaternary ammonium salts of the typedescribed above. Variquat 66®, for example, comprises bothhydroxyl-substituted, ethoxylated tertiary fatty amines andhydroxyl-substituted ethoxylated quaternary ammonium salts. According toinformation provided by the manufacturer, the tertiary amine componentof this product is quaternerized, in part, and associated with thecounterion of the quaternary ammonium compound.

Preferred ethoxylated tertiary fatty amines for use in forming theantistatic composition of the invention include those of the formula##STR7## wherein y and z may be the same or different and are eachintegers from 2-16; and R₉ represents a normal or branched, saturated orunsaturated, C₆ -C₁₈ aliphatic group.

The preferred amine reactants having 2-16 repeating ethoxy units arecharacterized in product information from the manufacturer as nominallyhaving eight repeating ethoxy units.

The antistatic agents of the invention are prepared by known syntheticprocedures, using conventional reaction conditions, as will beexemplified below. The progress of the reaction may be monitored, ifdesired, by standard analytical techniques, e.g., infra-redspectroscopy.

Although the resulting reaction mixture can advantageously be applied,as is, to static-prone substrates, various additives may be included inthe reaction mixture to impart certain desirable properties to theresultant composition. The selection of appropriate additives willdepend to some extent on the manner in which the antistatic agent isincorporated into the substrate. Additives may include solvents, e.g.,isopropanol, surfactants such as ethoxylated nonylphenol (Trycol® 6974,available from Henkel Corporation), and the like. The appropriate amountof any specific additive to be included in the antistatic composition ofthe invention may readily be determined on the basis of routine testing.

The antistatic composition may be applied to natural or synthetictextile materials or mixtures of natural and synthetic materials, e.g.,nylon, rayon, acetate, rayon-cellulosic materials such as celluloseacetate-proprionate, cellulose-butyrate, cotton, linen, jute, ramie,wool, mohair and glass, e.g., fiberglass and fiberglass insulation. Thetextile materials may take virtually any form, including individualfibers, yarns, woven materials such as fabrics, cloth, carpets, rugs andupholstery and non-woven materials such as felts, bats and mats. In thecase of fiberglass strand or fiberglass insulation, the composition maybe applied externally as a finish or as part of a sizing composition.

The plastic substrates in which the antistatic agents of the inventionmay be beneficially incorporated include, for example, nylon(polyamide), polycarbonate, polyphenylene oxide, polyester, polyolifinsand the like, and blends thereof with various other compatible resins.

Representative examples of suitable thermoset materials which have beentreated using the antistatic composition of the invention are apolyester/polyether (Lomod®, available from Ashland Chemical Company), anylon/polyester (Bexloy®, available from E. I. DuPont de Nemours) and apolyurethane (Bayflex®, available from Mobay Chemical). Commercial sheetmolding compound, composed, for example, of a polyester filled withcalcium carbonate and chopped glass fibers, has also been treated withthe antistatic agents described herein.

Examples of materials which may be treated with the antistatic agent ofthe invention include thermoplastic linear polyethylene, andthermosetting alkyd, polyester and epoxy resins.

Incorporation of the antistatic composition into any given substratewill depend on the manner of manufacturing the substrate and may includesurface application via padding, immersing, roller coating, spraycoating and the like. The composition may also be blended with resinousmaterials which thereafter undergo various forming operations, e.g.,extrusion or molding to yield the finished substrate. Of course, formedsubstrates may also be surface coated. For textile materials, thepreferred form of application is by immersion, i.e., running the textilesubstrate through a bath of the antistatic composition. The appropriatemode of application may be selected by those skilled in the art in viewof the overall dimensions or geometrical configuration of the surface tobe treated. In any case, the mode of application should be one whichcauses a reasonably uniform thickness of the antistatic composition tobe deposited on the treated surface. For flat surfaces, such as sheet orstrip material, this may usually be accomplished most readily throughthe use of rollers or squeegees. The application temperature of thecomposition may vary over a wide range, but is preferably from 5° to 50°C.

Coating thickness may vary from as little as a monolayer to any desiredthickness, although generally no advantage is achieved by thicknessgreater than about 20 microns, while the cost of the treatment isincreased. Normally, the coating thickness for textile, thermoplastic orthermoset substrates to acquire an acceptable level of conductivity willbe at least 0.2 microns. In operation, processing variables willnormally be determined based upon the desired coating thickness to beobtained.

Any excess antistatic agent is typically removed from the treatedsubstrate before drying. The excess may be removed by a gentle waterrinse, air knife blow drying, immersion in water (with or withoutagitation), air pressure or ultrasound. Drying may be carried out by,for example, circulating air, infra-red oven drying, or mechanicaldrying. While room temperature drying may be employed, it is preferableto use elevated temperatures to decrease the amount of drying timerequired.

Under normal operations, it is desirable to use elevated oventemperatures and warm air streams of velocity insufficient to disturbthe wet film. From a practical standpoint, the drying temperature shouldbe well below the softening point of the surface undergoing surfacetreatment.

Surfaces treated in accordance with the present invention arecharacterized by a surface resistance of between about 10⁶ ohms andabout 10¹² ohms, a 90% electrostatic charge decay time of 10 seconds orless, or both. Devices for measuring surface resistance or electrostaticcharge decay time are commercially available from various sources andtheir use is exemplified hereinbelow.

Static or charge dissipation is a function of the surface resistanceproperty of the material. Surface resistance is inversely related to thesurface conductivity. In other words, the lower the value of surfaceresistance, the better the ability of an applied charge to dissipate toground. Surface resistance testing is complementary to electrostaticcharge decay measurement tests which measure the time required to anapplied charge to dissipate to a predetermined cut-off value. Inelectrostatic charge decay testing, the lower the time required fordissipation of the applied charge, the high the surface conductivity.Hence, low resistance values will generally correlate with low staticdecay times.

Surfaces treated by the method of the invention will readily accept anelectrostatically applied coating material, as will be exemplifiedbelow.

The following examples are provided to describe the invention in furtherdetail. These examples, which set forth the best mode presentlycontemplated for carrying out the invention, are intended to illustrateand not to limit the invention.

EXAMPLE I

Preparation of Antistatic Composition

An antistatic composition in accordance with this invention was preparedby reacting 75 grams of ethyl bis(polyethoxyethanol) tallow ethylsulfate ammonium salt with 25.5 grams of trifluoroacetic in the presenceof anhydrous MgSO₄ (8 grams) in a 200 ml round bottom reaction vesselequipped with a mechanical stirrer. No solvent was used in conductingthe reaction. A small amount of H₂ SO₄ (approximately 0.4 grams) wasadded as a catalyst. The reaction was heated at 100° C. for 45 minutes.The reaction temperature was then raised to 150° C. for 30 minutes. TheMgSO₄ in the mixture settled to the bottom of the reaction vessel. Thereaction mixture was filtered through Whatman 5 qualitative filter paperto obtain a clear amber liquid, having a specific gravity of 1.1-1.2grams/ml.

The reaction was followed by infrared spectroscopy. The productexhibited the convergence of bands about 950 and 915 cm⁻¹ to a band at935 cm⁻¹ with a weak shoulder at 920 cm⁻¹. There was also a convergenceof a band at 700 cm⁻¹ and its shoulder at 690 cm⁻¹ into a single sharpband at 700 cm⁻¹. An intensification of bands at 855, 780 and 735 cm⁻¹was also observed. The 1020 cm⁻¹ band shifts/looses intensity to a newband at 1040 cm⁻¹. Intensity changes in the 1260 cm⁻¹ band are difficultto assign, but in general, it appears to lose intensity.

Other antistatic compositions in accordance with this invention can beprepared following the general procedure described above, butsubstituting a longer chain perfluoroaliphatic acid for trifluroaceticacid and/or quaternary ammonium compounds, such as methylbis(polyethoxyethanol) coco ethoxylated chloride ammonium salt orEmerstat 6660A (polyethoxy coco ether amine diethyl sulfate ammoniumsalt), for the quaternary ammonium salt exemplified herein.

The reaction described immediately above may be carried out in thepresence of a solvent, if desired. Thus, 100.2 grams of ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt was dissolvedin 151 grams of toluene and the solution was heated under nitrogen toapproximately 110° C. for forty-five minutes. To the heated solution wasadded 34 grams of trifluoroacetic acid and heating was continued at113°-115° C. for about three hours. A water-toluene azeotrope wasdistilled and collected. The residual toluene was vacuum stripped fromthe reaction mixture at 77 millibar and 40° C.

A C¹³ analysis was performed on the resultant reaction mixture. Thespectrum of trifluoroacetic acid exhibited a quartet centered at ˜116ppm due to the CF₂ carbon and another quartet at ˜161 ppm attributableto the carbonyl carbon. This spectrum evidences a doublet of quartetsfor the carbonyl and CF₂ carbons which suggest that the reaction mixturecontains both starting material (i.e., unreacted acid) as well asproduct. If it is assumed that the weaker quartet in the ˜116 ppm regionis attributable to product, the result is a 1:1 ratio between the CF₂resonances from the product to that of the CH₃ carbon of the quaternaryammonium salt reactant. These data suggest the presence of a monoesterof the acid and the quaternary ammonium salt reactant. Strong resonancesobserved in the 122-140 ppm region were due to toluene.

The solvent used in this reaction should be carefully selected tominimize loss of reactants, especially in the case of relatively lowboiling compounds, such as trifluoroacetic acid.

EXAMPLE II

Surface Application of Antistatic Composition to Nylon Yarns andStability Testing

Nylon yarn samples were treated with the following five antistaticcompositions of the present invention: (1) a reaction product of ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt andheptafluorobutyric acid; (2) a reaction product of methylbis(polyethoxyethanol) coco ethoxylated chloride ammonium salt andheptafluorobutyric acid; (3) a reaction product of ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt andtrifluoroacetic acid; (4) a reaction product of ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt andnonadecafluorodecanoic acid; and (5) a reaction product of ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt andperfluoroheptanoic acid. The treated yarn samples possessed satisfactorysurface resistance (log (R) in the range of 8 to 10), which weremaintained after washing with water in the case of four of the fiveantistatic compositions (1-3 and 5)

The protocol for making the resistance measurements was analogous tothat described in "Resistance and Static Behavior of Textile Surfaces"by S. P. Hersh, Chapter 6 of Surface Characteristics of Fibers andTextiles, Part 1, ed. by M. J. Schick; Marcel Dekker, Inc. (1975) .

EXAMPLE III

External Application of Antistatic

Composition to Nylon 6,6 Panels and Determination of Resistance

4"×6" panels composed of Nylon 6,6 (supplied by Advanced CoatingTechnologies, Inc., Hillsdale, Mich.) were used to determine the staticdissipative effect of a composition of the invention, measured in termsof surface resistance.

The antistatic composition used in this example was prepared accordingto the procedure described in Example I, above.

Each of three nylon 6,6 test panels was separately treated with (1) theantistatic composition of the invention, (2) ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt alone, and (3)an unreacted mixture of trifluoroacetic acid and ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt, according tothe following test procedure. The nylon 6,6 panels were initially rinsedwith deionized water and wiped with isopropanol. After determining thatthe resistance of the cleaned panels was greater than or equal to 10¹⁵ohms/per square (ohms/□), one of the treating agents was swabbed ontothe panel. The swabbed panel was heated to 120° F. for 10 minutes andany excess antistatic agent was wiped from the panel with Kimwipe®tissue until no visible traces of the agent remained. The wiped panelwas rinsed under a running stream of deionized water for 10 seconds pertreated side, then dried at 120° F. for 10 minutes.

The surface resistance of each set of panels was measured at a specifiedrelative humidity using a Milli-to-2 Wide Range Resistance Meter with anElectro-Tech Systems, Inc., Model 803A, surface/volume resistance probe.The resistance values measured twenty-four hours after treatment andstorage at 45% relative humidity are set forth in the following table I.

                  TABLE I                                                         ______________________________________                                        Ethyl bis(polyethoxyethanol)                                                                      8.0 × 10.sup.13 ohms/square                         tallow ethyl sulfate ammonium                                                 salt                                                                          CF.sub.3 CO.sub.2 H/ethyl bis                                                                     3 × 10.sup.13 ohms/square                           (polyethoxyethanol) tallow                                                    ethyl sulfate ammonium salt                                                   Ethyl bis(polyethoxyethanol)                                                                      6.9 × 10.sup.12 ohms/square                         tallow ethyl sulfate ammonium                                                 salt esterified with CF.sub.3 COOH                                            ______________________________________                                    

The data in Table I show that the surface resistance improves when ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt is esterifiedwith trifluoroacetic acid. The poorest surface resistance recorded forthe fluorinated ester was two-and-a-half times more conductive than thebest surface resistance recorded in the case of either the ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt alone or anunreacted mixture of ethyl bis(polyethoxyethanol) tallow ethyl sulfateammonium salt and trifluoroacetic acid. The data show overlap at the twosigma--90% confidence level.

The results of the foregoing tests show that the surface resistance ofthe Nylon 6,6 panels treated with the antistatic composition of theinvention is improved and longer lasting, as compared to Nylon 6,6panels treated with ethyl bis(polyethoxyethanol) tallow ethyl sulfateammonium salt alone or a mixture of ethyl bis(polyethoxyethanol) tallowethyl sulfate ammonium salt and trifluoroacetic acid.

EXAMPLE IV

Surface Treatment of Panels with Antistatic Agent of the Invention andComparative Agents and Determination of Conductivity

4"×6" thermoplastic panels composed of either Lomod, Bexloy, or Bayflexand panels of two different automotive sheet molding compounds (SMC A &B) composed of polyester ester filled with calcium carbonate and choppedglass fibers were used as test substrates to determine the staticdissipative effect of the antistatic compositions of the invention. Thepanels of sheet molding compound differed from one another with respectto surface roughness, by reason of the application of a surfacemodifying "low profile" agent to one of the panels.

Each panel was initially rinsed in tap water, towel dried, and immersedfor 2 minutes in an aqueous solution of antistatic agent followed byimmersion for 2 seconds in deionized water, a 30 second tap water sprayrinse at 12 psi and oven drying at 120° F.

In carrying out this experiment, a panel of each substrate type wastreated with the following: (1) a mixture composed of stearyldimethylammonium ethyl sulfate which is sold by PPG/Mazer Chemicalsunder the trademark Larostat® 451 and potassium hydrogen phthalate,which mixture is the subject of U.S. Pat. No. 5,219,493; (2) ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt; (3) anantistatic composition of the invention comprising the reaction productof trifluoroaceitc acid and ethyl bis(polyethoxyethanol) tallow ethylsulfate ammonium salt; (4) an antistatic composition of the inventioncomprising the reaction product of heptafluorobutyric acid and ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt; (5) methylbis(polyethoxyethanol) coco ethoxylated chloride ammonium salt; (6) anantistatic composition of the invention comprising the reaction productof trifluoroacetic acid and methyl bis(polyethoxyethanol) cocoethoxylated chloride ammonium salt; and (7) an antistatic composition ofthe invention comprising the product of the reaction ofheptafluorobutyric acid and methyl bis(polyethoxyethanol) cocoethoxylated chloride ammonium salt.

Conductivity of the treated panels was measured by electrostatic chargedecay at a specified relative humidity using an electrostatic chargedecay meter (Model 406C, Electro-Tech Systems, Inc., Glenside, Pa.)according to the following procedure. A five KV charge (either positiveor negative) was applied to the panel, then the charge was allowed todissipate to a prescribed percentage of the initial charge (in this case90% charge dissipation). The time in seconds required for decay of thecharge to the specified level was measured. Conductivity of the treatedpanels is inversely proportional to the time required for the prescribedelectrostatic decay to occur.

The results of electrostatic charge decay measurements on the treatedpanels are set forth in the following table II.

                  TABLE II                                                        ______________________________________                                        SUBSTRATE*                                                                    Treating                                                                      Agent   SMC A    SMC B     Lomod Bexloy Bayflex                               ______________________________________                                        1       3.78     RC        0.10  21.2   10.0                                  2       5.05     RC        0.20  28.4   20.4                                  3       3.48     RC        0.15  22.4   1.19                                  4       1.58     13.99     0.12  12.28  0.28                                  5       RC       RC        0.08  26.4   9.51                                  6       6.91     RC        0.07  30.0   2.56                                  7       3.16     RC        0.08  15.8   0.34                                  ______________________________________                                         *5 KV  500 V decay times measured in seconds                                  RC  Residual Charge                                                      

The test results set forth in Table II indicate that the panels treatedwith the antistatic composition of the invention exhibit superiorelectrostatic charge decay as compared with the other agents tested.

EXAMPLE V

Effect of Varying the Chain Lengths of the Fluorine-ContainingConstituents of the Antistatic Agent on Substrate Conductivity

4"×6" panels of the same substrates tested in Example IV, above, wereused to determine the effect on conductivity of the treated panelsresulting from varying the chain length of the fluorinated carboxylicacid constituent of the antistatic composition of the invention.

In carrying out this test, an untreated panel of each substrate type wasused as a control.

A test panel of each substrate type was treated with (1) ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt; (2) areaction product of trifluoroacetic acid and ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt; (3) areaction product of heptafluorobutyric acid and ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt; (4) areaction product of perfluoroheptanoic acid and ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt; (5) areaction product of nonadecafluorodecanoic acid and ethylbis(polyethoxyethanol) tallow ethyl sulfate ammonium salt; (6) methylbis(polyethoxyethanol) coco ethoxylated chloride ammonium salt; (7) areaction product of trifluoroacetic acid and methylbis(polyethoxyethanol) coco ethoxylated chloride ammonium salt; and (8)a reaction product of heptafluorobutyric acid and methyl bis(polyethoxyethanol) coco ethoxylated chloride ammonium salt.

Conductivity of the treated panels was measured by electrostatic chargedecay for a specific relatively humidity (R.H. of 50%) using anelectrostatic charge decay meter in the manner described in Example IV,above.

The results of static decay measurements on the panels treated asdescribed above are set forth in the following table III.

                  TABLE III                                                       ______________________________________                                        SUBSTRATE*                                                                    Treating                                                                      Agent   Bexloy   Lomod   Bayflex                                                                              SMC A  SMC B                                  ______________________________________                                        Control 21.2     0.10    10.0   3.78   RC                                     1       28.4     0.20    20.4   5.05   RC                                     2       22.4     0.15    1.19   3.48   RC                                     3       12.3     0.12    0.28   1.58   14.0                                   4       7.11     0.11    1.00   12.2   RC                                     5       1.08     0.17    2.56   11.6   RC                                     6       26.4     0.08    9.51   RC     RC                                     7       30.0     0.07    2.56   6.91   RC                                     8       15.8     0.08    0.34   3.16   RC                                     ______________________________________                                         *5 KV500 V decay time measured in seconds                                     RC  Residual Charge                                                      

The test results set forth in Table III show that panels treated withthe antistatic compositions formed from fluorocarbons of relativelygreater chain length and quaternary ammonium salts of relatively longerchain hydrocarbons tend to impart higher conductivity (i.e., shorterdecay times) to the treated panels.

EXAMPLE VI

Surface Treatment of Thermoplastic Substrate with Antistatic AgentFollowed By Application of Electrostatic Coating

A thermoplastic airbag cover (Izumi), measuring 4×5 inch, was used as asubstrate to determine the effect of the antistatic agent of theinvention on the conductivity of such a substrate and the adhesion of asubsequently applied electrostatic coating. The same substrate, whichwas not treated with the antistatic agent of the invention, was used asa control.

In carrying out the test, the substrate was treated with an antistaticagent resulting from the reaction of a quaternary ammonium ethyl sulfatesalt mixture of 10 weight percent CH₃ CH₂ N(CH₂ CH₂ OH)₃ ⊕ and 90 weightpercent C_(n) H_(2n+1) OCH₂ CH₂ N(CH₂ CH₃)(CH₂ CH₂ OH)₂ ⊕ (Emerstat®6660A) where n=12 to 14 with trifluoroacetic acid in a toluene solutionto which a small amount of base material was added. The reaction productwas distilled to remove a water-toluene azeotrope formed during thereaction.

An antistatic treatment bath was made up comprising 50 grams of theresultant antistatic agent, 50 grams isopropanol, 2 grams ethoxylatednonylphenol (Trycol® 6974) and 898 grams deionized water. The bath washeated to 125° F. to disperse the antistatic agent. The substrate wasimmersed in the treatment bath for 5 minutes, then spray rinsed forabout 30 seconds at 10-15 psi with deionized water and oven dried for 5minutes at 120° F.

Conductivity of the treated substrate was measured by electrostaticcharge decay at a predetermined relative humidity (40%) using anelectrostatic charge decay meter (Model 406C, Electro-Tech Systems,Glenside, Pa.) according to the following procedure. A 5 KV charge(either positive or negative) was applied to the substrate, then thecharge was allowed to dissipate to the extent of 90% of the initialcharge. The time in seconds required for decay of the charge to the 90%level was measured. Conductivity of the test panel is inverselyproportional to the time required for the prescribed electrostatic decayto occur. For the treated substrate, the measured decay time was 0.5seconds, indicating that the conductivity was maintained after aqueousrinse.

The treated substrate exhibited fair wrap around by a subsequent coatingof enamel which was electrostatically applied to the substrate. Bycomparison, the untreated substrate exhibited no wrap around afterelectrostatic application of the same enamel coating.

While it is apparent that the various embodiments of the inventiondisclosed and exemplified are well suited to fulfill the above-statedobjects, it will be appreciated that the invention is susceptible tomodifications, variations and change without departing from the spiritof the invention, the full scope of which is delineated by the appendedclaims.

What is claimed is:
 1. A method for dissipating an electrostatic chargeon a static-prone substrate comprising incorporating into said substratean antistatic agent of the formula Q--L--(R--X)_(d), wherein Qrepresents a normal or branched, saturated or unsaturatedperfluoroaliphatic radical, L represents an ester or an ether linkage, Rrepresents an alkylene-oxyalkylene or an alkylene-poly(oxyalkylene)group, and X represents at least one quaternary ammonium group of theformula ##STR8## and, optionally, a tertiary amine group of the formula##STR9## wherein R₁ and R₄ independently represent --(C₂ H₄ O)_(f) --Z,Z being H, Q or ##STR10## wherein Q is as defined above, f being aninteger from 1 to 50, R₂ represents a C₁ -C₄ alkyl group, R₃ and R₅independently represent a normal or branched, saturated or unsaturatedC₆ -C₂₂ aliphatic group, A represents an organic or inorganic anion andd is 1 or 2 in an amount effective to impart to said substrate a surfaceresistance value in the range of from about 10⁶ to about 10¹² ohms, a90% electrostatic charge decay time of 10 seconds or less, or both.
 2. Amethod as claimed in claim 1, wherein said antistatic agent isincorporated into a textile substrate.
 3. A method as claimed in claim2, wherein said antistatic agent comprises an ester having as itsreactive components at least one acid of the formula (C_(q)F_(2q+1))--COOH, wherein q represents an integer from 1-17, and at leastone quaternary ammonium compound of the formula ##STR11## wherein s andw may be the same or different and are each integers from 2-16; t is 1or 2; R₈ represents a normal or branched, saturated or unsaturated C₆-C₁₈ aliphatic group; A represents an anion selected from the groupconsisting of halide, sulfate and lower alkyl sulfate, and at least onetertiary amine of the formula ##STR12## wherein y and z may be the sameor different and are each integers from 2-16; R₉ represents a normal orbranched, saturated or unsaturated, C₆ -C₁₈ aliphatic group; and atleast one of (i) said acid in unreacted form, (ii) said quaternaryammonium compound in unreacted form, and (iii) said tertiary amine inunreacted form is incorporated into said textile substrate.
 4. A methodas claimed in claim 3, wherein said antistatic agent is externallyapplied to said substrate.
 5. A method as claimed in claim 4, whereinsaid antistatic agent is applied by passing said textile substratethrough a bath comprising said antistatic agent.
 6. A method as claimedin claim 3, wherein said antistatic agent is internally incorporatedinto said substrate.
 7. A method as claimed in claim 1, wherein saidantistatic agent is incorporated into a formed, thermoplastic substrate.8. A method as claimed in claim 7, wherein an antistatic agentcomprising an ester having as its reactive components at least one acidof the formula (C_(q) F_(2q+1))--COOH, wherein q represents an integerfrom 1-17, and at least one quaternary ammonium compound of the formula##STR13## wherein s and w may be the same or different and are eachintegers from 2-16; t is 1 or 2; R₈ represents a normal or branched,saturated or unsaturated C₆ -C₁₈ aliphatic group; A represents an anionselected from the group consisting of chloride, sulfate and lower alkylsulfate, and at least one tertiary amine of the formula ##STR14##wherein y and z may be the same or different and are each integers from2-16; R₉ represents a normal or branched, saturated or unsaturated, C₆-C₁₈ aliphatic group; and at least one of (i) said acid in unreactedform, (ii) said quaternary ammonium compound in unreacted form, and saidtertiary amine in unreacted form is incorporated into said thermoplasticsubstrate.
 9. A method as claimed in claim 8, wherein said antistaticagent is externally applied to said substrate.
 10. A method as claimedin claim 8, wherein said antistatic agent is internally incorporatedinto said substrate.
 11. A method as claimed in claim 1, wherein saidantistatic agent is incorporated into a formed thermoset substrate. 12.A method as claimed in claim 11, wherein an antistatic agent comprisingan ester having as its reactive components at least one acid of theformula (C_(q) F_(2q+1))--COOH, wherein q represents an integer from1-17, and at least one quaternary ammonium compound of the formula##STR15## wherein s and w may be the same or different and each integersfrom 2-16; t is 1 or 2; R₈ represents a normal or branched, saturated orunsaturated C₆ -C₁₈ aliphatic group; A represents an anion selected fromthe group consisting of chloride and lower alkyl sulfate, and at leastone tertiary amine of the formula ##STR16## wherein y and z may be thesame or different and are each integers from 2-16; R₉ represents anormal or branched, saturated or unsaturated, C₆ -C₁₈ aliphatic group;and at least one of (i) said acid in unreacted form, (ii) saidquaternary ammonium compound in unreacted form, and (iii) said tertiaryamine in unreacted form is applied to said thermoset substrate.
 13. Amethod as claimed in claim 11, wherein said antistatic agent isexternally applied to said substrate.
 14. A method as claimed in claim11, wherein said antistatic agent is internally incorporated into saidsubstrate.
 15. An article of manufacture comprising a substrate selectedfrom the group consisting of a textile substrate, a formed,thermoplastic substrate and a formed, thermoset substrate havingincorporated therein the antistatic agent of the formulaQ--L--(R--X)_(d), wherein Q represents a normal or branched, saturatedor unsaturated perfluoroaliphatic radical, L represents an ester or anether linkage, R represents an alkylene-oxyalkylene or analkylene-poly(oxyalkylene) group, and X represents at least onequaternary ammonium group of the formula ##STR17## and, optionally, atertiary amine group of the formula ##STR18## wherein R₁ and R₄independently represent --(C₂ H₄ O)_(f) --Z, Z being H Q or ##STR19##wherein Q is as defined above, f being an integer from 1 to 50, R₂represents a C₁ -C₄ alkyl group, R₃ and R₅ independently represent anormal or branched, saturated or unsaturated C₆ -C₂₂ aliphatic group, Arepresents an organic or inorganic anion and d is 1 or
 2. 16. An articleof manufacture as claimed in claim 15, wherein an antistatic agentcomprising an ester having as its reactive components at least one acidof the formula (C_(q) F_(2q+1))--COOH, wherein q represents an integerfrom 1-17, at least one quaternary ammonium compound of the formula##STR20## wherein s and w may be the same or different and are eachintegers from 2-16; t is 1 or 2; R₈ represents a normal or branched,saturated or unsaturated C₆ -C₁₈ aliphatic group; A represents an anionselected from the group consisting of halide and lower alkyl sulfate,and a tertiary amine of the formula ##STR21## wherein y and z may be thesame or different and are each integers from 2-16; R₉ represents anormal or branched, saturated or unsaturated, C₆ -C₁₈ aliphatic group;and at least one of (i) said acid in unreacted form, (ii) saidquaternary ammonium compound in unreacted form, and (iii) said tertiaryamine in unreacted form is incorporated into said substrate.
 17. Anarticle of manufacture as claimed in claim 16, wherein said antistaticagent comprises an ester having as its reactive componentstrifluoroacetic acid, at least one quaternary ammonium compound selectedfrom the group consisting of bis(polyethoxy ethanol) tallow ammoniumsalt; methyl bis(polyethoxy ethanol) coco ammonium salt and polyethoxycoco ether amine diethylsulfate ammonium salt and at one least tertiaryamine selected from the group consisting of bis(polyethoxy ethanol)tallow amine and bis(polyethoxy ethanol) coco amine, and at least one of(i) said acid in unreacted form, (ii) said quaternary ammonium compoundin unreacted form, and (iii) said tertiary amine in unreacted form.